JPS59205304A - Bactericidal fungicides - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the known substituted 5-t-butyl-1,3,4
-Thiadiazol-2-yl-ureas for sterilization of grains
For use as fungicides.

The use of substituted 5-tert-butyl-1,3,4-thiadiazol-2-yl-ureas as herbicides is known (DE 2,423,469) See Section 2,614゜6-842, German Publication Specification No. 3,113,328 Oyobi C, A, 88.84,572 (1978))
, and generally have fungicidal activity (fungicidal activity).
al action) is also mentioned.

Furthermore, it is also known that organic sulfur compounds such as zinc ethylene-1,2-bis-(dithiocarbamate) have bactericidal and fungicidal properties (R, Unigra (We
G.I.E.R., "Plant Protection and Pest Control Agents", Springel-Verlag, Peidelberg, New York, 1970, vol. 2, p. 65 et seq.).

However, the activity of these compounds is not always completely satisfactory in certain fields of application, especially at low application rates and concentrations.

General formula CI) 1 [wherein R represents t-butyl mono- or polysubstituted by halogen, R1 and R2 independently of each other represent hydrogen or alkyl, and R3 represents alkyl or halogenoalkyl ] Substituted 5-t-butyl-1,3,4-thiadiazol-2-yl-ureas are effective against fungi and molds (f
It has now been found that it has potent fungicidal suicidal fungicidal activity against (K. ung+).

Surprisingly, substituted 5-t-butyl-1,3,4-thiadiazol-2-yl-ureas of the general formula CI) are known from the prior art and have the same direction of activity. For example, zinc ethylene-1,2-bis-
It has particular activity against fungal pathogens of larger grain diseases than thiocarbamates such as (dithiocarbamates).

Therefore, N-substituted 5-tert-butyl-1 according to the invention,
The use of 3,4-thiadiazol-2-yl-ureas provides an advantage to the art.

Formula CI) is the substituted 5-t used according to the invention
-Butyl-1,3,4-thiadiazol-2-yl-ureas are given general definitions.

Suitable compounds of formula (I) represent one of the following or CIk M'-C'-CH3CH,X', 9- in which Xl represents halogen, in particular fluorine, chlorine or bromine, and X2 represents hydrogen or halogen, in particular fluorine, chlorine or bromine, R1 and R2 independently of each other represent hydrogen or straight-chain or branched alkyl of up to 4 carbon atoms, and R3 represents straight-chain or Branched alkyls having up to 4 carbon atoms or straight-chain or branched sulfalogenoalkyls having up to 4 carbon atoms and up to 5 identical or different halogens, especially fluorine, chlorine or bromine atoms; represents something.

Particularly very preferred compounds of formula (I) are those in which R represents one of the radicals 10-CH3CH,CH,CICH,cH,CH,C1 and R1 and R2 are independently hydrogen. or methyl, and R3 is methyl, ethyl, n- and i-propyl, n-
2i-1S- and t-butyl, fluoromethyl, chloromethyl, fluoroethyl, chloroethyl, CE
.

CICH-C- CH3 ! f'-1 CH.

F-CH! -C- The following compounds of general formula (I') may be mentioned as individual examples: 11- -N 12 One example C'H.

1 F-CB, -C-CE B C1i.

C’H3 CM3 2 C'L-CM, -C-CB, HCM.

slow C’li.

CM.

3　C”1-C11,-C-BRCM.

C.B.

CM.

4 F-CM, -C-CM, Hn-C,Ii
.

CM.

CM.

5 F-C'H, -C-CMllE i-C,li
.

summer C.E.

13- continuation: CM.

6 F-C1f2-C-HCM, CM.

" CE3 CM.

7 C1, CM-C-C1l II CM
sCM.

CB, F ■ 8 CE-C-C11llII CB3 CM, F CM, C1 9CH, -c-CM, HC113 Summer ch, ct C1i.

10 F-CM, -C-CM, Hn-C,H.

CM.

continuation: Example Number RRIRRRI CM.

11 CL-CH, -C'-HII-Cbird-C
hi, -C1C'li.

CD.

12 C1-C bird-(,’-HCM, CM.

11,’#.

C7/.

13 F-CB, -C-HHCM.

■ CH.

CM, F " 14 CH, -C-B HCM.

C1i, F substituted 5-t of formula (I) used according to the invention
-Butyl-1,3,4-thiadiazol-2-yl-ureas are known. They are, for example, the corresponding 2-amino-1,3,4-thiadiazole derivatives of the formula (17) [wherein R and R1 have the above meanings] of the formula (m) 0=C=N-R2 or o=c=NR” (m) [
in which R2 and R8 have the abovementioned meanings;
V) A diimitation isocyanate of the formula (Vl) 1 in which R has the meaning as shown in - or R and R have the meaning as shown in L, and Hal represents fluorine, chlorine or bromine], optionally in the presence of a diluent such as ethyl acetate, optionally an acid binder such as triethylamine,
and optionally in the presence of a catalyst such as dibutyltin laurate at a temperature between 20°C and 120°C.
9, DE 2,614.842, DE 3,113°328 and C, A, Dan 1.84,572r [1978]).

The active compounds of formula (1) according to the invention have strong fungicidal and fungicidal activity and can be used in practice for controlling undesirable fungi and molds. The active compounds are suitable for use as plant protection agents, in particular as fungicides for cereals, including corn and rice.

In plant protection, the fungicidal fungicides are used to treat Plasmodiophoromycetes (Plasmodiophoromycetes).
eteS), Oomycetes, Chytridiomycetes, Zygomycetes, Asc.
omycetes), Basidiomycetes
:ete18-s), t-3J: Deuteromyc
It is used to control insects (etes).

Owing to the good tolerability of the active compounds by plants in the concentrations required for controlling plant diseases, it is possible to treat the above-ground parts of plants, the growing stems and seeds, as well as the soil.

The active compounds according to the invention are effective against organisms that cause diseases of cereals, such as Puccinia rotomycosis of wheat.
econdita), as well as for the control of Pyrenophorateles (Pyreno phorateles), an organism that causes cereal diseases.
phora tereS) and Cochliobolus 5ativus
), against organisms that cause powdery mildew of cereals, and against Pellicularia 5asaki, an organism that causes diseases of rice.
kii) with success.

The active compounds can be present in the usual preparations, e.g. solutions, emulsions,
Suspensions, powders, foams, coatings, granules, aerosols, natural and synthetic substances impregnated with active compounds, as well as very fine capsules in polymeric substances and supplementary coating compositions, as well as e.g. Fumigation cartridge,
It can be converted into formulations used with combustion devices such as fumigation cans, fumigation coils, etc., as well as ULV cold mist and warm mist formulations.

These formulations are prepared in a known manner, for example by combining the active compounds with fillers, optionally using surfactants, emulsifiers and/or dispersants and/or blowing agents.
That is, they can be produced by mixing with liquid solvents, liquefied gases under pressure, and/or solid carriers. When using water as extender, organic solvents can be used as co-solvents, for example. The following are mainly suitable as liquid solvents: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylene. or methylene chloride, aliphatic hydrocarbons such as cyclohexane, or paraffins such as mineral oil distillates, alcohols such as butanol or glycols and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl Ketones or cyclohexanone, or strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water, liquefied gaseous extenders or carriers, are liquids that are gaseous at normal temperature and pressure, such as aerosol propellants. halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. Solid carriers include 1*, for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground minerals, such as highly dispersed Silicic acid, alumina and silicates are suitable solid carriers for zero granules.
For example, crushed and fractionated natural rocks, such as calcite, marble, eavestone, granite and dolomite, as well as synthetic granules of inorganic and organic powders, and granules of organic substances, such as sawdust, etc. Scraps, coconut husks, corncobs and tobacco stalks are suitable. Emulsifiers and/or blowing agents include, for example, nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, such as alkylaryl polyglycol ethers, alkyl sulfonates. , alkyl sulfates, arylsulfonates, and albumin hydrolysis products are suitable. Suitable dispersants are, for example, lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules and latexes such as gum arabic, polyvinyl alcohol and polyvinyl acetate can be used in the formulation 22-.

Colorants, such as inorganic pigments, such as iron oxide, titanium oxide and Prussian blue, and organic dyes, such as alizarin dyes, azo dyes* and metal phthalocyanine dyes, and micronutrients, For example, salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain from 0.1 to 95% by weight, preferably from 0.5 to 95% by weight.
90% by weight of active compound.

The active compounds according to the invention can be used in combination with other known active compounds, such as fungicides, fungicides, bactericides, insecticides, acaricides, stericides, in formulations or in various use forms. It can be present in mixtures with insecticides, herbicides, poulticides, growth factors, plant nutrients and soil structure improvers.

The active compounds according to the invention may be used as such or in the form of their preparations or application forms prepared from them by further dilution, such as prepared solutions, solutions, emulsions, suspensions, powders, liniments and granules. It can be used in the form of a drug. They can be applied by conventional methods such as dispersion, dipping, atomization, atomization, atomization, evaporation, injection, slurry formation,
It is used by brushing, powdering, granulating, dry application, wet application, wet application, slurry application or coating.

In the partial treatment of plants, the active compound concentration in the use form can be varied within a substantial range. They are generally between 1 and 0.0001% by weight, preferably 0.0001% by weight.
It is between 5 and 0.001 weight φ%.

In seed treatment, 0.001 to 5 per kg of seeds.
An amount of active compound between 0 g, preferably between 0.01 and Log is generally required.

In soil treatment, o, oo at the site of action.

between 0.01 and 0.1% by weight, preferably between 0.0001 and 0.0001% by weight.
Active compound concentrations of between 2% by weight are generally required.

EXAMPLE The compound shown here was used as a comparative substance in the following usage example: Ethylene-1,2-bis-(dithiocarbamate)
.

Puccinia test (wheat)/protective solvent: 100
Part by weight of dimethylformamide emulsifier: 0.25 part by weight of alkylaryl polyglycol ether To prepare a suitable formulation of the active compound, 1 part by weight of the active compound is mixed with the above amount of solvent and the above amount of emulsifier; The concentrate was then diluted with water to give a concentration of ψ.

25- To test the protective activity, young plants were inoculated with a spore suspension of Puccinia recondita in a 0.1% strength agar solution. After the spore suspension has dried, the plants are sprayed with the active compound preparation until drippings. Plants were kept in a culture room at 20° C. and 100% relative atmospheric humidity for 24 hours.

To promote the development of Aspergillus spores, the plants were placed in a greenhouse at a temperature of about 20° C. and a relative atmospheric humidity of about 80%.

Evaluation was performed 101] after inoculation.

In this test, compounds according to the Preparation Examples below, for example, showed clearly superior activity compared to the prior art.

26- hit n
% -i
(:t's Ll')
Rihe
to to 0
0 C1(B
6 at2
9-12? - □□li Example 卆'', 3 g (0.11 mol) of methyl isodiad is 18.9
g (0.1 mol) of 2- (1.

dimethyl-2-fluoroethyl)-5-methimino-1,
3,4-thiadiazole and 3 drops of dibutyl-tin laurate were added dropwise to a solution of 100 ml of ethyl acetate. The reaction mixture was heated under reflux for 3 hours. After cooling, the reaction solution was washed with citric acid and saturated sodium bicarbonate solution, dried over sodium sulfate-L, and evaporated. The residue was recrystallized from ethyl acetate/petroleum (1:1).

5.7g (63.8% of theory) melting point 16-162°
1-[5-(1,1-dimethyl28--2-fluoroethyl)-1,3,4-thiadiazol-2-yl]-1,3-dimethyl-urea of C was isolated.

Sesumi 11℃ Nihino a) H,C 80.3g (0,525 mol) of phosphorus oxychloride was added to 51.
5 g (0.5 mol) of 4-methyl-thiosemicarbazide, 64.6 g (0.5 mol) of 92.8% strength 2.2-
dimethyl-3-fluoropropionic acid and 425 m
1 of dioxane under reflux over 35 minutes. The reaction mixture was heated under reflux for 4 hours until hydrogen chloride evolution was complete. After the mixture had cooled, the solution was decanted and heated on a water bath to reduce the residue to 1°2.
Dissolved in 50 ml of water. The solution was adjusted to pH 1 l with 50 g of sodium hydroxide and extracted with chloroform. The extracts were washed with water and then evaporated.

69.4g (73.4% of theory) melting point 78-80°C
2-(1,1-dimethyl-2-fluoroethyl)-5
-Methylamino-1,3,4-thiadiazole was obtained.

b) CH3 F-CH, -C-CO-OR 680 g (17 mol) of sodium hydroxide at 2°26
Add dropwise to 0 ml of solution in water, then add 200 g (1,
7 mol) of 3,3-dimethyl-4-fluorobutane-2
-one was added at 0°C to 5°C and the mixture was
Stirred at 0°C for 2 hours. It was then filtered, the bromoform phase was separated, and the aqueous phase was decolorized using a 2M sodium disulfite solution. After acidification with 850 ml of concentrated hydrochloric acid, the aqueous phase was extracted with methylene chloride. The organic phase was dried over sodium sulphate and then evaporated. 153.6 g (69.9% of theory) of 2,2-dimethyl-, melting point 71°C
3-fluoropropionic acid was obtained.

Patent applicant: Bayer Akchengesellschaft 32-

Claims (1)

[Scope of Claims] 1. At least one type of formula (1) [wherein R represents t-butyl mono- or polysubstituted with halogen, and RL and R2 each independently represent hydrogen or alkyl; and R3 represents alkyl or halogenoalkyl. A fungicide and fungicide for controlling grain diseases. C-CH3, where xl represents halogen, x2 represents hydrogen or halogen, and R1 and R2 independently of each other are hydrogen or a straight or branched chain having up to 4 carbon atoms alkyl and R3 is straight-chain or branched alkyl having up to 4 carbon atoms or halogen having up to 4 straight-chain or branched carbon atoms and up to 5 identical or different halogen atoms; at least one substituted 5-t of formula CI) according to claim 1, such that it represents alkyl;
A bactericidal/fungicidal agent for controlling diseases of grains, characterized by containing -butyl-1°3.4-thiadiazol-2-yl-urea. -CH, -C- where xl represents fluorine, chlorine or bromine; X2 represents hydrogen or fluorine, chlorine or bromine; alkyl of up to 4 and R3 is straight-chain or branched alkyl of up to 4 carbon atoms or straight-chain or branched alkyl of up to 4 carbon atoms and up to 5 of the same or different fluorine, chlorine; or substituted 5-t-butyl-L, 3,4-thiadiazol-2-yl- of the formula (I) according to claim 1, which represents at least one halogenoalkyl having a bromine atom. A fungicidal fungicide for controlling diseases of grains, characterized by containing urea. 4, R1 and R2 independently of each other represent hydrogen or methyl, and R3 is methyl, ethyl, n- and i-propyl, n-
1i-1S- and t-butyl, fluoromethyl, chloromethyl, fluoroethyl, chloro1-methyl
At least one formula according to claim 1, in which CH8 ct-cH, -c- F-CH, -C- R represents one of the groups CH3CHll CH, F CH, CH3CH, C1 A bactericidal and fungicidal agent for controlling diseases of grains, characterized by containing the substituted 5-t-butyl-1,3,4-thiadiazol-2-yl-urea of (I) Agents. 5. Substituted 5- of formula (I) according to claim 1 for controlling fungal pathogens of cereal diseases
t-Butyl-1,3,4-thiadiazol-2-yl-
Use of ureas. 6. Substituted 5-t-butyl-1,3,4-thiadiazol-2-yl-ureas of the formula (I) according to claim 1 are added to fungi and/or their habitats. A fungus that causes diseases of grains, which is characterized by its ability to act on certain locations.
How to control fungal pathogens. 7. Mixing substituted 5-t-butyl-1,3,4-thiadiazol-2-yl-ureas of formula (I) according to claim 1 with an extender and/or a surfactant. A method for producing a bactericidal and fungicide for controlling diseases of grains, which is characterized by: